Production of high quality diesel fuel



Feb. 11, 1947.

H. H. MEIER 2,415,700

PRODUCTION OF HIGH QUALITY DIESEL FUEL Filed Dec. 26, 1944 I GondnswrFeed I Hector Stock 1 2 Hydroforrning Zone *loffinutc *9 Hydrpgen 6solvent I Ruflincm reaction I 9 30 van lo attraction uwa' Entree? x feEnema? ')A ATTORNEY.

I N D "1 J PATENT OFFICE. Q

PRODUCTION OF HIGH QUALITY DIESEL FUEL v Herbert H. Meier, BaytownpTex., asslgnor to Standard Oil Development Company, a corporation ofDelaware ApplicationDecemberZG,1944, SerlalNo. 569,189

' 30laims. '(Ci.196-13) The present invention is directed to a methodflde. In general. catalys s containing 6th gr p for producing improvedDiesel fuels. metal oxides. pr fe y i conjunction with $111- It is knownthat the quality of gas oil, as a min are seti et ry- Diesel fuel,increases as its content of 'straight- In the accompanying drawing thesingle figchain paraflins and naphthenes with only a'limwe is a frontelevation in diagrammatic form' ited number of side chains increases.There are .of one type of apparatus which may be emvirgin gas oils whichare predominately straightployed for the practice of the Present vechain paraflins and naphthenes containing only tion.

minor amounts (from 51:0 10%) of aromatics. It R rring to the drawing indetail, h m r l is postulated that the condensed ring naphthenes 10 idesignates a fe iine f r th s ilte be are less desirable than thesimpler naphthenes as processed. This feed line discharges into ahycomponents of a Diesel fuel. For example, it is dr formin ch mb 2.after P ing throu h a believed that naphthenes with only one ring and Dea 3 W e e t e gas oil is bro ght to t a long paraflinic side chain aremore effective desired reaction temperature. Ahead of the re- .fuelsthan those with two or more'rings. That i n h r is a ran h lin Q f r ltin is to say, these desirable gas oils contain effective hydrogen intothe feed line.

naphthenes and those of simpler character are f desired. the feed to ybe initially solof greater value in Diesel fuels. vent extracted -forthe remo'valof aromatics. It is understood that the quality of thesevirgin For this p p a branch line 5 s ected to gas oils, or any othergas .oils having a similar line I and discharges into the lower end ofan makeup, can be improved by solvent extraction extraction vessel 6.Selective solvent, such as with solvents's uch as phenol, fur-fural,sulfur di ph nol, i fe into t upp r part of vessel 5 oxide,nitrobenzene, chlorinated hydrocarbons throu h line I and extract iswithdrawn from and the like which have a selective solvent act e w 'e tf t r e 3. This Vestion for aromatics. These selective solvents do '25Se] Will O r y be P v W hinternal eonnot, however, serve to remove theundesirable I tact equipment to facilitate mixing of the feednaphthenes. stock and the solvent. Rafinateleaves the top According .tothe present invention a gas oil of vessel 6 through line 9 and returnsto line ihaving a composition of the type referred to is The efiillentfr m the y in h mber i converted into a more valuable Diesel fuel byintroduced into the lower part of an extraction being subjected to ahydroforming operation calve sel I a te flr tp t ou a co de ser culatedto convert the simpler naphthenes into ii. If desired, t condenser ay eemitted aromatics whereby the resulting aromatics can because in theextraction tower t e as oil vap s be solvent extracted from the gas oil.The 113 Will be condensed during the extraction P ess droforming iscarried out for this purpose under which in this case will be partiallyvaporphase comparatively mild conditions compared to those and P t yliquid P e S ve employed in naphtha reforming. For example, vent isintroduced into the upp Portion of the operating temperature should bebetween sel i 0 through l ne n extr v is W thdrawn about 850 and 950,the pressure should be befrom the bottom thereof through line 53.Rafiltween about 300 and 350 pounds per square in h; 40 nate leaves thetop of the vessel through line it. the feed rate should be between about0.5 and In some cases the hydroforming operation will 3.5 volumes of gasoil per volume of catalyst per result in the conversion of some of theparaflins hour, and hydrogen should be employed in an to oleflns. Whenthis occurs, the ramnate from amount ranging between about 1000 and 3000the extraction vessel i0 should be subjected to cubic feet per barrel.The catalyst may be seconventional hydrogena n 'i P p Of lected from afairly large list of catalyst found reconverting the olefins back toparaflins. This suitable for hydroforming operations with thehydrogenation, when required, will be of the low qualificationthathydroforming catalysts which temperature type in which a simplehydrogenatend to facilitate the cyclicization of paraflins tioncatalyst, such as metallic nickeLis employed. "should be avoided. Asuitable catalyst is one 5 The details of this type of hydrogenation arecomposed of molybdenum oxide and gamma well known and need notbe-further elaborated alumina having a low soda content. Metal sulon.

fides may also be employed either alone or in As a result of theprocesses described above, admixture with each other, such as forexamthe pour. point of the gas oil may be substanple, a mixture ofnickel sulfide and tungsten sultially raised. If reduction of this pourpoint is has been made of the term hydroforming."

desired, it is preferred to accomplish it by the addition of a pourpoint depressant of the type readily available on the market rather thanby dewaxing.

Throughout the specification and claims use In the sense thathydroforming is used is describing the present invention, it issynonymous with catalytic reforming in-the presence of hydrogen andshall be understood to mean a process of catalytic reforming carried outin the presence of added or recirculated hydrogen or gases containinghydrogen under such conditions that there is no overall net consumptionof free hydrogen or there is an overall net production of free hydrogen.

The nature and objects of the present invention having been thusdescribed and illustrated;

what is claimed as new and useful and is desired to be secured byLetters Patent is:

1. A method for improving the Diesel quality of a gas oil containingparafilns and low quality naphthenes which comprises subjecting the gasoil in admixture with hydrogen to the action of a hydroforming catalystfree from components which promote the cyclicization of paramns at atemperature between about.850 and 950 F. under elevated pressure andwith a feed rate between 0.5 and 3.5 volumes of gas oil per volume ofcatalyst per hour and subjecting the product of this catalytic operationto solvent extraction for the removal therefrom of aromatics.

2. A method according to claim 1 in which REFERENCES CITED The followingreferences are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,366,490 Cloud Jan. 2, 19452,268,094 Russell Dec. ,30, 1941 2,271,214 Welty Jan. 27, 1942 2,339,108Pier et a1 Jan. 11, 1944 2,361,080 Bolt et al. -1- Oct. 24, 1944 FOREIGNPATENTS Number Country Date 850,899 French Sept. 18, 1939 373,670Italian Aug. 1, 1939 441,104 British Jan. 13, 1936 423,001 British 1,Jan. 23, 1935

